US8110137B2 - Process for manufacturing a plastic-based cellular structure - Google Patents

Process for manufacturing a plastic-based cellular structure Download PDF

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Publication number
US8110137B2
US8110137B2 US12/293,305 US29330507A US8110137B2 US 8110137 B2 US8110137 B2 US 8110137B2 US 29330507 A US29330507 A US 29330507A US 8110137 B2 US8110137 B2 US 8110137B2
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Prior art keywords
cellular structure
extrusion direction
process according
during
temperature
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US12/293,305
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English (en)
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US20090107621A1 (en
Inventor
Claude Dehennau
Dominique Grandjean
Philippe-Jacques Leng
Frederic Beullekens
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Solvay SA
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Solvay SA
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Assigned to SOLVAY (SOCIETE ANONYME) reassignment SOLVAY (SOCIETE ANONYME) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LENG, PHILIPPE-JACQUES, BEULLEKENS, FREDERIC, DEHENNAU, CLAUDE, GRANDJEAN, DOMINIQUE
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/022Particular heating or welding methods not otherwise provided for
    • B29C65/028Particular heating or welding methods not otherwise provided for making use of inherent heat, i.e. the heat for the joining comes from the moulding process of one of the parts to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/11Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels comprising two or more partially or fully enclosed cavities, e.g. honeycomb-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/05Particular design of joint configurations
    • B29C66/10Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112Single lapped joints
    • B29C66/1122Single lap to lap joints, i.e. overlap joints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/40General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43Joining a relatively small portion of the surface of said articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/40General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43Joining a relatively small portion of the surface of said articles
    • B29C66/434Joining substantially flat articles for forming corner connections, fork connections or cross connections
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311Thermal properties
    • B29C66/73117Tg, i.e. glass transition temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7377General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline
    • B29C66/73771General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being amorphous
    • B29C66/73772General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being amorphous the to-be-joined areas of both parts to be joined being amorphous
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7377General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline
    • B29C66/73773General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being semi-crystalline
    • B29C66/73774General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being semi-crystalline the to-be-joined areas of both parts to be joined being semi-crystalline
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
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    • B29C66/82Pressure application arrangements, e.g. transmission or actuating mechanisms for joining tools or clamps
    • B29C66/826Pressure application arrangements, e.g. transmission or actuating mechanisms for joining tools or clamps without using a separate pressure application tool, e.g. the own weight of the parts to be joined
    • B29C66/8266Pressure application arrangements, e.g. transmission or actuating mechanisms for joining tools or clamps without using a separate pressure application tool, e.g. the own weight of the parts to be joined using fluid pressure directly acting on the parts to be joined
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    • B29D24/002Producing articles with hollow walls formed with structures, e.g. cores placed between two plates or sheets, e.g. partially filled
    • B29D24/005Producing articles with hollow walls formed with structures, e.g. cores placed between two plates or sheets, e.g. partially filled the structure having joined ribs, e.g. honeycomb
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    • B32B2479/00Furniture
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to a process for manufacturing a plastic-based cellular structure, more particularly a plastic-based anisometric cellular structure.
  • a requirement encountered in many (automotive, civil engineering, naval, etc.) industries consists in optimizing the mechanical properties/weight ratio of the structures used.
  • Numerous processes have been developed for achieving this objective, and in particular for lightening plastic structures. Most of these processes use either the mechanical formation of macroscopic cells (by assembly of solid or molten streams in order to form cellular structures known as “honeycomb” structures), or by physical formation of microscopic cells by release or expansion of a gas (expansion or foaming using physical or chemical blowing agents).
  • Patent (1) The process described in Patent (1) consists in:
  • the cellular structures obtained are solid on exiting the cooling chamber and considering, in addition, the presence of a take-off unit downstream from the die, their geometry is such that their longitudinal axis is oriented in the extrusion direction.
  • the flexural modulus of all the cellular structures is substantially higher in the transverse direction (perpendicular to the extrusion direction) than in the longitudinal direction (“machine” direction, parallel to the extrusion direction), limiting their interest for certain applications and preventing them from being wound onto a reel. This is because when it is desired to bend them longitudinally, they deform transversely, which constitutes a serious practical drawback when long length cellular structures are continuously extruded.
  • the cellular structures obtained still in the molten or pasty state on exiting the die, most often have an elliptical cross section, the main axis of which is oriented in the extrusion direction.
  • the flexural modulus of all the cellular structures is substantially higher in the transverse direction than in the longitudinal direction (“machine” direction); the height of the elliptical surface of revolution forming the wall of each cell is thus limited and generally substantially lower than the longitudinal axis of said cell.
  • the cellular structures obtained according to this process therefore suffer from the same drawbacks as those obtained according to the process described in Patent (1).
  • the object of the present invention is to solve these problems and especially to make it possible to obtain anisometric cellular structures based on a plastic whose properties are more isotropic, which are less dense than known cellular structures and which may be wound onto a circular reel.
  • the present invention therefore relates, primarily, to a process for manufacturing a plastic-based cellular structure comprising:
  • plastic is understood to mean any amorphous or semi-crystalline thermoplastic polymer (P), including thermo-plastic elastomers and also blends thereof.
  • polymer is understood to mean both homopolymers and copolymers (especially bipolymers or terpolymers). Examples of such copolymers are, in a non-limiting manner: random copolymers, linear block copolymers, other block copolymers and graft copolymers.
  • amorphous polymer is understood to mean any thermoplastic polymer (P) predominantly having a disordered arrangement of the macromolecules that form it.
  • this term is understood to mean any thermoplastic polymer that contains less than 30% by weight, preferably less than 10% by weight of crystalline phase (that is to say, the phase characterized by a melting endotherm during differential thermal analysis (DSC) measurements).
  • thermoplastic polymer is under-stood to mean any thermoplastic polymer (P) having, in a large proportion, a chemically and geometrically regular arrangement of the macromolecules that form it.
  • this term is understood to mean any thermoplastic polymer that contains more than 30% by weight, preferably more than 50% by weight, of crystalline phase (that is to say the phase characterized by a melting endotherm during differential thermal analysis (DSC) measurements).
  • DSC differential thermal analysis
  • T g glass transition temperature
  • T m melting temperature
  • T g is the temperature below which a polymer mass has several properties of inorganic glass, including hardness and rigidity. Above the T g , the polymer mass has plastic or elastic properties and it is said to be in the rubbery or elastomeric state.
  • T m is also called the flow temperature in the case of amorphous polymers and the straightforward melting point when it is a question of semi-crystalline polymers.
  • T m which is rather, in practice, a temperature zone or range
  • thermoplastic polymer or copolymer whose T m is below the decomposition temperature may be used in the process according to the present invention.
  • Synthetic thermoplastics that have a melting range spread over at least 10° C. are particularly well suited. Examples of such materials are those that have a polydispersity of their molecular weight.
  • polystyrene resin polyvinyl halides
  • PVDF polyvinylidene halides
  • thermoplastic polyesters polyarylethersulphones such as polyphenylsulphones (PPSUs), polyketones, polyamides (PA) and copolymers thereof.
  • polyarylethersulphones such as polyphenylsulphones (PPSUs), PAs, PVCs and PVDFs have given good results.
  • a polyarylethersulphone denotes any polymer of which at least 5% by weight of the repeat units are repeat units (R) corresponding to one or more formulae comprising at least one arylene group, at least one ether group (—O—) and at least one sulphone group [—S( ⁇ O) 2 —].
  • the polyarylethersulphone may especially be a polybiphenylethersulphone, a polysulphone, a polyethersulphone, a polyimidoethersulphone or else a blend composed of polyarylethersulphones chosen from the aforementioned polyarylethersulphones.
  • composition based on at least one thermoplastic polymer (P) (known hereinafter more simply as “composition”) used in the process according to the invention may be formed from a single polymer, from a blend of polymers or copolymers or from a blend of polymer material(s) with various additives (stabilizers; plasticizers; inorganic, organic and/or natural or polymer fillers, etc.). This composition may have undergone various treatments such as expansion, orientation, etc.
  • a blowing agent may also be present, enabling expanded or foamed cellular structures to be produced.
  • the blowing agent according to this variant of the present invention may be of any known type.
  • gases are CO 2 , nitrogen, steam, hydrofluorocarbons or HFCs (such as the 87/13 wt % CF 3 —CH 2 F/CHF 2 —CH 3 mixture sold by Solvay as SOLKANE® XG87), hydrocarbons (such as butane and pentane) or a mixture thereof.
  • a “chemical” blowing agent that is to say a substance (or a mixture of substances) dissolved or dispersed in the plastic and which, under the effect of the temperature, releases the gas or gases which will be used for the expansion of the plastic.
  • azodicarbonamide and mixtures of sodium bicarbonate with citric acid. The latter give goods results.
  • blowing agent used in the process according to this variant of the invention must be optimized, especially according to its nature, to the properties (especially dynamic viscosity) of the polymer present and to the desired final density. In general, this content is greater than or equal to 0.1%, preferably 0.5%, or even 1%.
  • polymers listed above may be added to by other polymers that are compatible or not with the latter and comprise, besides the optional plasticizers, the usual additives used for processing polymers, such as, for example, internal and external lubricants, heat stabilizers, light stabilizers, inorganic, organic and/or natural fillers, pigments, etc.
  • the implementation of the process according to the invention means that parallel lamellae of the composition based on at least one thermoplastic polymer (P) is extruded continuously during a step (a) through a die containing a plurality of parallel slots.
  • extrusion devices that are suitable for this implementation are described in the Patent (1) and in the Patent Application (2).
  • the device described in Patent (1) comprises an extruder feeding the molten composition to a coat-hanger die consisting of several parallel slots each intended for the continuous formation of a lamella, each slot being delimited by two parts in the shape of cones, produced from a thermally insulating material, cut into each of which is a groove.
  • the device described in the Patent Application (2) essentially comprises:
  • These knives are generally positioned in parallel vertical planes and approximately equidistant apart. Between them they define flow channels having, in the flow direction of the molten composition, a convergent first part and thereafter, a substantially straight part, the latter forming the side walls of each constituent slot of the die.
  • the implementation of the process according to the invention then means carrying out a step (b) during which, on exiting the die and in successive alternations, the spaces between two adjacent lamellae are subjected to an injection of a fluid (f) and to a vacuum, the two sides of a same lamella being, for one side, subjected to the action of the fluid (f) and, for the other side, to the action of the vacuum, and inversely during the following alternation, in order to produce deformation of the lamellae and to weld them in pairs with formation, in a plane approximately parallel to the extrusion direction, of a cellular structure whose constituent cells extend perpendicular to the extrusion direction.
  • step (b) Practical embodiments of step (b) are also described, for example, in Patent (1) and in Patent Application (2).
  • the fluid (f) is a coolant for the cellular structure in the process of being formed, and is, in particular, water. It means that each groove, cut into each cone-shaped part of each slot of the die, is connected, successively, to a vacuum source and to a coolant source. Shaping of the cellular structure is carried out via two shaping assemblies, consisting of conical parts that are additional to the cone-shaped parts of the die and that are mounted vertically on the die, that is to say in the direction of the cells of the structure that has to be formed, in order to allow control of its thickness.
  • the two shaping assemblies define, by their facing surfaces, the support zones of the two faces of the cellular structure perpendicular to the cells.
  • a chamber for shaping and cooling the cellular structure This chamber being tubular with a rectangular cross section and having a height equal to the height of the structure to be obtained, in the direction of the cells of the latter, and having a width equal to that of the structure.
  • the fluid (f) is a gas, for example an inert gas, a mixture of inert gases or air. It requires the presence, in the device for extruding the composition, of two short sizing units generally being in the form of metal blocks placed on the front face of the die comprising the slots determined by the vertical knives, the front face which may be coated with a sheet of insulating material as mentioned above. These sizing units are placed on either side of the die slots, one above them and the other below them. They can generally be moved vertically, in opposite directions, in order to define the height of the extruded lamellae and consequently the height of the final cellular structure.
  • a gas for example an inert gas, a mixture of inert gases or air.
  • chambers are cut out in each of these sizing units, starting from which chambers are tubular ducts that terminate in generally circular orifices emerging near the spaces between the die slots and therefore, during the implementation of the process according to the invention, near the spaces between the extruded lamellae.
  • Each chamber of each of these sizing units is alternately connected to a vacuum pump or to a compressed gas circuit.
  • the spaces between two adjacent extruded lamellae are subjected, in successive alternations, to an injection of compressed gas and to a vacuum, the two sides of any one lamella being, for one side, subjected to the action of the compressed gas and, for the other side, to the action of the vacuum, and inversely during the following alternation, in order to produce deformation of the lamellae and weld them in pairs with formation, in a plane approximately parallel to the extrusion direction, of a cellular structure, the constituent cells of which extend perpendicular to the extrusion direction.
  • Each sizing unit is preferably set at a temperature below T struct , but above T struct minus 80° C., preferably above T struct minus 50° C., even above T struct minus 25° C., where T struct is a structural temperature that corresponds to T g if the composition comprises an amorphous polymer and to T m if the composition comprises a semi-crystalline polymer.
  • the gas may be heated.
  • the temperature of the gas is preferably greater than or equal to the processing temperature (T p ) of the plastic minus 100° C., preferably greater than or equal to T p minus 50° C., even greater than or equal to T p minus 20° C.
  • step (b) described in Patent (1) preferably applies to amorphous thermoplastic polymers (P) having a dynamic melt viscosity (measured conventionally via measurements of the shear stress and strain on a rheogoniometer) at their processing temperature (that is to say at the temperature at which they are extruded in order to be converted into cellular structures) and at an angular velocity of 0.1 rad/s of less than 2000 Pa ⁇ s, preferably of less than 1000 Pa ⁇ s.
  • these polymers have, in addition, a T g , measured conventionally by DSC (according to the ISO 11357-2 standard), of less than 60° C., preferably of less than 50° C.
  • Non-limiting examples of amorphous polymers which may fit the definitions and limitations above are thermoplastic elastomers, and also blends thereof; thermoplastic polyesters and homopolymers and copolymers derived from vinyl chloride, and also blends thereof.
  • thermoplastic elastomers and also blends thereof
  • thermoplastic polyesters and homopolymers and copolymers derived from vinyl chloride and also blends thereof.
  • homopolymers and copolymers plasticized by monomeric or polymeric plasticizers are more particularly preferred.
  • plasticizers mention may be made of phthalates, sebacates, adipates, trimellitates, pyromellitates, citrates and polyesters such as poly( ⁇ -caprolactone) and blends thereof.
  • These homopolymers and copolymers generally contain at least 10 parts and up to 75 parts by weight of plasticizer per 100 parts by weight of polymer.
  • plasticizer polymers known as “internal plasticization polymers”, that are obtained by copolymerization of vinyl chloride with plasticizer comonomers, such as for example ethylhexyl acrylate, or else by copolymerization with grafting onto the polymers known as “elasticizers” such as poly( ⁇ -caprolactone).
  • step (b) described in Patent Application (2) is preferably applied to thermoplastic polymers (P) having a melt viscosity (measured at the processing temperature and at 0.1 rad/s) greater than or equal to 2500 Pa ⁇ s, preferably greater than or equal to 3000 Pa ⁇ s.
  • This practical embodiment is also advantageously applied to compositions whose semi-crystalline or amorphous constituent polymer(s) (P) have a glass transition temperature (T g ) which may reach and even surpass 80° C., preferably between about 40 and about 60° C.
  • T g glass transition temperature
  • This practical embodiment also gives good results with plastic compositions comprising a blowing agent, such as those mentioned above, which enable expanded or foamed cellular structures to be produced. This is because the fact of using a compressed gas instead of water as the fluid (f) makes it possible, through the least cooling, to improve the drawing of the cells of the foam and by doing this to improve its texture.
  • steps (a) and (b) of the process according to the present invention are adapted in particular to the nature of the plastic-based composition. It should especially be ensured that the temperature of this composition at the die exit is adapted so as to be able to weld the cells, to expand the composition where appropriate, etc, in the absence of deformation due to gravity. It should also be ensured that the alternating pressure and vacuum values, and also the duration of the cycles, are adapted so as to optimize this welding. In practice, a pressure greater than or equal to 0.5 bar relative, or even greater than or equal to 1.5 bar, is preferably used. This pressure is generally less than or equal to 6 bar, even less than or equal to 4 bar or even more so less than or equal to 2 bar.
  • the vacuum is generally greater than or equal to 100 mmHg absolute, or even greater than or equal to 400 mmHg.
  • the duration of the cycles is generally greater than or equal to 0.3 s, even greater than or equal to 0.4 s, and preferably greater than or equal to 0.5 s. This duration is preferably less than or equal to 3 s, even less than or equal to 2 s and even more so less than or equal to 1 s.
  • the implementation of the process according to the invention may advantageously comprise, after carrying out step (b) and before carrying out step (c), an optional step (b2) during which the cellular structure obtained in step (b) is brought to a temperature (T 1 ) such that T g ⁇ T 1 ⁇ T g +40° C., T g being the glass transition temperature of the thermoplastic polymer (P) if it is amorphous, or brought to a temperature (T 2 ) such that T m ⁇ T 2 ⁇ T m ⁇ 50° C., T m being the melting point of the thermoplastic polymer (P) (measured according to the ASTM D 3417 standard) if it is semi-crystalline.
  • Step (b2) may be carried out under static or dynamic conditions, that is to say that it may be carried out on the cellular structure that is immobilized after its extrusion (and its shaping) or on the cellular structure that is kept moving after its extrusion and its shaping.
  • Step (b2) may be carried out by using any known means for heating a plastic: it is possible to use, for example, an electric oven, an oven having a liquid or solid fuel, and it is possible to heat the plastic by irradiation, by infrared radiation, etc.
  • T 1 is between (T g +10° C.) and (T g +35° C.). If T 1 is too low (typically, less than the T g of the polymer), the polymer is too viscous and if T 1 is too high, the polymer is too fluid to be able to be correctly used by the process according to the invention.
  • this variant of the invention generally means reheating the structure after its extrusion (step (b)).
  • T 2 is between (T m ⁇ 10° C.) and (T m ⁇ 40° C.). If T 2 is too high, the melt behaviour of the polymer does not allow it to be correctly converted into the final cellular structure according to the process of the invention. Typically, it must approach the crystallization temperature of the polymer. In the case of a continuous process, this variant of the invention may be carried out without reheating the structure after its extrusion.
  • the process according to the invention comprises a step (c) during which the cellular structure, preferably thermally conditioned according to the optional step (b2), is transversely drawn, that is to say drawn perpendicular to the extrusion direction.
  • step (c) during which the cellular structure, preferably thermally conditioned according to the optional step (b2), is transversely drawn, that is to say drawn perpendicular to the extrusion direction.
  • the scope of the invention also extends to the processes in which a cellular structure manufactured continuously according to the successive steps (a) and (b) is first stocked or stored in order to then subject it, successively or, at least partly, simultaneously, to the optional step (b2) and step (c). Finally, the scope of the invention also extends to the processes in which during step (c), successively or simultaneously, a transverse drawing (perpendicular to the extrusion direction) and a longitudinal drawing (parallel to the extrusion direction) are carried out.
  • the transverse draw ratio to which the cellular structure is subjected during step (c), expressed by the ratio of the final working width of the cellular structure after drawing to its initial width, is at least 1.2/1, preferably 1.5/1, particularly 2/1, even 2.5/1.
  • the drawing may be carried out by any known technique. It is possible, for example, to use the drawing lines sold by Brückner Maschinenebau GmbH, in which a transverse drawing and a longitudinal drawing of the cellular structure may be carried out simultaneously or successively.
  • the drawing lines are generally composed of a system of chains on which jaws are placed that clamp the cellular structure via its two side ends and that move apart during the advancement of said cellular structure, as soon as this cellular structure has reached the temperature set in step (b2)—when the latter step is carried out—this temperature possibly being reached, as has already been said, before or during step (c).
  • the term “working width after drawing” is understood to mean the marketable width without the drawing jaws.
  • the practical drawing conditions, transverse and optionally longitudinal, exerted during step (c), are preferably chosen so that the ratio of the apparent flexural moduli measured on the final cellular structure (three-point bending test according to the ISO 1209-2 standard), parallel to the extrusion direction (longitudinal direction) and perpendicular to the extrusion direction (transverse direction) is less than 10, preferably less than 5, most particularly less than 2.
  • This ratio may even, in the case of cellular structures based on certain semi-crystalline thermoplastic polymers (P), such as PP for example, be less than one.
  • the thickness of the cellular structure may be levelled out (that is to say that the height of the constituent cells may be made uniform) using any suitable device, such as heated cylinders for example.
  • the cellular structure obtained may be cooled by ambient air, by blowing with a jet of cold air, by spraying with a water mist, etc. A jet of cold air gives good results. After cooling, the edges that have possibly been bitten into by the jaws of the drawing line may be cut off and recycled.
  • the cellular structure obtained may then be taken up by a take-off unit.
  • the haul-off speed and the extrusion rate will be optimized, especially according to the size and thickness of the cells, and also to the desired shape.
  • the final cellular structure On leaving the take-off unit, the final cellular structure may easily be wound onto a reel. Alternatively, it may be subjected to a surface treatment (a corona treatment, for example), so as to improve the adhesion properties thereof in particular, and to be lined with a nonwoven or with top and bottom facings. At the end of these optional operations, the final panel is cut both lengthwise and widthwise into sheets of the desired dimensions and stored.
  • a surface treatment a corona treatment, for example
  • the production scrap may be taken up either before the finishing operations, or afterwards, and recycled back into production.
  • the shape of the cells of the structure formed by the process of the invention is most often approximately polygonal, preferably approximately hexagonal, the sides of the polygon formed being non-isometric, that is to say that the lengths of the sides are unequal.
  • These generally hexagonal cells most often have a ratio of their length L (in the extrusion direction) to their width 1 (in the extrusion plane but along a direction perpendicular to that of the extrusion) of less than 2.5, preferably of less than 1.5, even equal to 1.
  • the length L of the cells is generally greater than or equal to 10 mm, even greater than or equal to 15 mm, but generally less than or equal to 30 mm.
  • the wall thickness of the cells is conditioned by the thickness of the walls of the base cellular structure and by the draw ratios imposed during the transverse and optionally longitudinal drawing. In practice, it is generally greater than or equal to 100 ⁇ m, even greater than or equal to 200 or to 250 ⁇ m. Advantageously, it does not however exceed 1 mm, even 0.8 and preferably 0.6 mm, so as not to weigh down the structure. The lower limit in fact depends on the embodiment of the die enabling the base cellular structure to be produced and on the draw ratios used.
  • the thickness of the walls of the drawn cellular structure is not less than 90% of the thickness of the walls of the base cellular structure, preferably it is not less than 95% of this thickness.
  • the present invention makes it possible to obtain cellular structures whose length can be varied over a very large measurement, and this being so with a wide range of plastic-based compositions and having adapted compositions.
  • the cellular structures obtained by the process according to the invention are advantageously used in the building industry (floors, lightweight ceilings, partitions, doors, concrete boxes, etc.), in furniture, in packaging (side protection, wrapping of objects, etc.), in motor vehicles (parcel shelf, door linings, etc.), etc.
  • These structures are particularly suitable for furniture and for buildings, for example for the construction of permanent shelters (habitations) or temporary shelters (rigid tents or humanitarian shelters, for example). They are also suitable as constituents of sports hall floors.
  • sandwich panels in which they are placed between two sheets called facings.
  • the latter variant is advantageous, and in this case it is possible to manufacture said sandwich panel by welding, bonding, etc., or any other method of assembling the facings and the core (used cold or hot, just after extrusion) that is suitable for plastics.
  • One advantageous way of manufacturing said sandwich panel consists in welding the facings to the cellular core. Any welding process may be suitable for this purpose, processes using electromagnetic radiation giving good results in the case of structures/facings that are at least partially transparent to the electromagnetic radiation. Such a process is described in application FR 03/08843, the content of which is incorporated for this purpose by reference in the present application.
  • a cellular structure 25 cm in width and 10 mm in height was extruded under the conditions and using the device that are described below:
  • a cellular structure was obtained having the following properties:
  • the flexural modulus of the cellular structure was substantially higher in the transverse direction than in the longitudinal direction, preventing them from being wound onto a reel, as when it is desired to bend them longitudinally, they deform transversely.
  • the cellular structure formed at the outlet of the device described in Example 1 was drawn transversely on a KARO drawing machine under the following conditions:
  • the process according to the invention made it possible to obtain a lighter cellular structure, of which the dimensions of the constituent cells were more isometric and of which the flexural moduli in the longitudinal direction and in the transverse direction were of the same order of size, enabling their winding onto a reel.
  • Example 3R The cellular structure formed at the outlet of the device described in Example 3R was transversely drawn on a KARO drawing machine under the conditions stated in Example 2.
  • the cellular structure formed at the outlet of the device described in Example 5 was transversely drawn on a KARO drawing machine under the following conditions:
  • this example illustrates the advantages obtained by the process according to the invention, this time in the case of a semicrystalline polymer: the cellular structure is lighter, the dimensions of the cells are more isometric and the flexural moduli in the longitudinal and transverse directions are of the same order of size.

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  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Thermal Sciences (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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FR0602705A FR2899145B1 (fr) 2006-03-29 2006-03-29 Procede pour la fabrication d'une structure alveolaire a base de matiere plastique
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FR2928712A1 (fr) * 2008-03-17 2009-09-18 Solvay Tube a paroi structuree en plastique, procede de fabrication dudit tube et utilisation particuliere de celui-ci.
FR2952323B1 (fr) * 2009-11-12 2011-12-09 Solvay Segment incurve a paroi multicouche en matiere plastique pour l'assemblage de tubes
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FR2961123B1 (fr) 2010-06-14 2012-06-29 Solvay Conformateur pour filiere d'extrusion de structures alveolaires a base de matiere plastique

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ATE446834T1 (de) 2009-11-15
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EP2001649B1 (en) 2009-10-28
WO2007110370A1 (en) 2007-10-04
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US20090107621A1 (en) 2009-04-30
FR2899145B1 (fr) 2008-05-09
CN101415532B (zh) 2012-05-30
KR20080104386A (ko) 2008-12-02
RU2428309C2 (ru) 2011-09-10
BRPI0709275A2 (pt) 2011-07-12
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